You could specify the relationship using a formula:
whether this is better or not is debatable.. it depends on your circumstances - one the one hand it ensures consistency, but on the other hand it will probably have a performance penalty when querying - so it really depends on your own specific case.
Another alternative is to use a trigger on insert into B to update the column in A. This has the downside of moving logic into the database, but it would ensure consistency without the potential performance penalty.
You could also achieve the equivalent of a trigger by using an NHibernate event to intercept saving B and then updating A - with the benefit of the logic remaining in your code, but the downside that any direct updates to the database could introduce inconsistency.
Of course both trigger options obfuscate the logic somewhat, as opposed to having a method on A or B that does the logic. I would personally probably put a method in A to add a new B and update the association, but then you would need to ensure that no-one updates the B collection directly and bypasses your method.